1, 2-dihydroxy-4, 5, 6, 7, 8, 8-hexahalo-4, 7-methano-3a, 4, 7, 7a-tetrahydroindane and method of preparing same



Patented Nov. 7, 1950 1,2 DIHYDROXY 4,5,B,7,8,8 HEXAHALO 4,7 METHANO3a,4,7,7a TETRAHYDRO-- INDANE- AND METHOD OF PREPARING SAME Simon n.Herzfeld and Morton Kleiman, Chicago, 111., assignors to VelsicolCorporation, Chicago,

IlL, acorporation of Illinois No Drawing. Application July 22, 1948,

Serial No. 40,153

7 Claims. 1

This invention relates to a new composition of matter and to a method ofproduction thereof.

More specifically, this invention relates to the preparation of amaterial having the structural formula:

wherein X is a halogen of the group consisting of chlorine, bromine andmixtures thereof.

According to The Ring Index" by Patterson and Capell, A. C. S. MonographSeries, No. 84, 1940, dicyclopentadiene, C10H12, is described as 4,7methano-3a,4,7,7a tetrahydroindene. Following this accepted system ofnomenclature, the compound above represented by structural formula canbe described (assuming the halogen atoms are all chlorine) as1,2-dihydroxy-4,5,6,- 7,8,8-hexachloro-4,7-methano-3a,4,7,'7atetrahydroindane.

Briefly, the process herein disclosed involves the oxidation of thecyclopentene ring in the Diels- Alder adduct of hexahalocyclopentadieneand cyclopentadiene (4,5,6,7,8,8-hexahalo-4,7methano-3a,4,7,7a-tetrahydroindene) to ultimately result in the glycolabove represented by structural formula. The reaction, starting with thematerials hexahalocyclopentadiene and cyclopentadiene may be representedas follows:

The Diels-Alder adduct of 9. hexahalocyclopentadiene andcyclopentadiene, the structure and name of which have been previouslymentioned. and the method for making same has been disclosed and claimedin the co-pending application of Herzfeld, Lidov and Bluestone. SerialNo. 639,416, filed January 5, 1946.

For the purpose of clarity and brevity only the Diels-Alder adduct ofhexachlorocyclopentadiene and cyclopentadiene will be hereinafterreferred to, although it is ex ressly understood that the adduct formedfrom hexabromocyclopentadiene or a mixed hexachloro-bromocyclopentadieneis fully applicable to the process of this invention. Further, the abovementioned adduct of hexachlorocyclopentadiene and cyclopentadiene willhereinafter be referred to as chlordene.

The oxidation of chlorine to the glycol may be effected, for example,'by treating chlordene with an organic peracid such as, perbenzoic,peracetic, or mono-perphthalic acid, and hydrolyzing the resultantoxidized product by means well known to the art. If the oxidation iscarried out in the presence of water, subsequent hydrolysis to form theglycol may be unnecessary. A specific example of such oxidation,followed b alcoholysis, to form the glycol derivative of chlordene i5hereinafter noted for the purpose of illustration.

As a non-fully equivalent alternative, the oxidation of chlordene to theglycol may be efiected by the use of such reagents as (1) cold, dilute,neutral, aqueous permanganate, (2) hydrogen peroxide and acetic acid, or(3) sodium chlorate in aqueous solution containing osmium tetroxide, allfollowed, where necessary, by hydrolysis to form the desired glycol.

The necessity for treatment of the oxidized chlordene to result in theglycol is apparent if the mechanism of oxidation be considered. Thus,oxidation, for example, with cold neutral aqueous permanganate resultsin a glycol as the first product and hence further treatment such ashydrolysis is unnecessary. However, the use of organic peracids willgenerally result in the formation of the oxide which must be hydrolyzedto result in the glycol. Such hydrolysis is known to the art and can beaccomplished in the ordinary way as, for example, by heating said oxidewith an aqueous or aqueous-alcoholic solution of an alkali such assodium hydroxide or potassium hydroxide. A1-

' kept at 45- C. for 44 hours.

moved in vacuo and the residue was dissolved 3 ternatively,- hydrolysismay be accomplished by heating the adduct in an aqueous acid such asaqueous sulfurichydrochloric or para-toluene sulfonic acid.-The-mechanism of this reaction a may be illustrated as follows:

Oxidation with organic peracids may result ,in mono-ester or diesterderivatives of the glycol instead of the oxide. Such ester derivativesmay also be hydrolyzed by the same means that the oxide is converted tothe glycol and thus it is not material as to which intermediate productis formed. If the ester derivatives of chlordene arise, conversion tothe glycol may also be e!- fected by alcoholysis, or, as it is sometimesreassass n.

ferred to, by the ester-interchange reaction. Al-

coholysis may be accomplished in the conventional' manner, for example,by treating the ester derivatives with an excess of an alcohol. preferably of a low molecular weight, such as methanol,

' ethanol, propanol, or ethylene glycol, which may act both as diluentand reactant, in the presence of a proper catalyst such as sulfuric orhydrochloric acid, or such basic compounds as sodium methoxide andsodium acetate. 1 As previously stated under certain aqueous oxidationconditions, hydrolysis cccurs'during the oxidation step and thus,subsequent hydrolysis, although not,

harmful, is unnecessary. It will be noted that in the specific examplesubsequentl cited, the di-ester derivative of chlordene was obtained byoxidation with an organic per-acid. In the speciflc example theconversion .to the glycol was accomplished by alcoholysis.

Preparation of 1,2dihydroxy-4,5,6,7,8,8-he;rachloro-4,7-methano-3a,4,7,7a-tetrahydroindaneA solution of 0.3 mol (102 g.) of chlordene,

0.6 mol (114 g.) of 40% peracetic acid, 100 ml. acetic anhydride and 350ml. of acetic acid was The solvent was rein benzene and then extractedwith aqueous sodium bisulfite to remove the last traces of the oxidizingagent. The benzene solution was dried over magnesium sulfate andconcentrated by evaporation. Hexane was added and thediacetoxyderivative'of chlordene crystallized from the mixture onstanding.

A solution of 60 g. of diacetoxychlordene, 600 m1. methanol, and 3 ml.concentrated hydrochloric acid was heated under reflux for 20 hours.

The alcohol was then removed by distillation and the residue was pouredinto cold water.

with water. talline solid melting at 139-140 C. was identified as thedihydroxy derivative of the Diels-Alder adduct ofhexachlorocyclopentadiene and cyclopentadiene.

The new product of the present invention is' valuable for use in thecontrol and destruction of insects. The product of this invention isalso useful as an intermediate in the preparation of other insecticidalcompositions derived from the I The solid product was recovered byfiltration and washed The purified material, a white crys- 4 presentparent compound by further halogens: tion and/or replacement of hydroxylgroups with chlorine atoms. Highly halogenated derivatives of the adductherein concerned may be prepared whichhave such uses as impregnants,iireproofing agents, etc.

We claim as our invention:

1.'A new composition of matter having the structural formula wherein Xis a halogen of chlorine, bromine and mixtures thereof.

2. A new composition of matter having the structural formula 3. Themethod of forming 1,2-dihydroxy- 4,5,6,7,8,8-hexahalo-4,7-methano-3a,4,7,7a-tetrahydroindane wherein the halogen atoms are ofthe group chlorine, bromine and mixtures thereof which comprisesoxidizing the cyclopentene ring containing carbon atoms 1, 2, 3, 3a and7a of 4, 5, 6, 7, 8, 8-hexahalo-4, 7-methano-3a, 4, 7,la-tetrahydroindene, with an organic peracid and hydrolyzing the thusoxidized material.

4. The method of'claim 3 where the 4,5,6,7,8,8-

hexahalo-4,7- methano 3a,4,7,7a tetrah'ydroindene is4,5,6,7,8,8-hexachloro 4,7-methano 3a,4,- 7,7a-tetrahydroindene.

5. The method of claim 3 where the. organic peracid is peracetic acid.

6. The method "of claim 3 where'the organic peracid is perbenzoic acid.7. The method of forming a new composition of matter which comprisesoxidizing the cyclopentene ring of4,5,6,7,8,8-hexahalo-4,7-methano-3a,4,7,7a-tetrahydroindene with anorganic peracid under essentially non-aqueousconditions in the presenceof an organic acid, and subjecting the thus oxidized material toalcoholysis.

SIMON H. HERZFELD. MORTQN KLEIMAN.

REFERENCES CITED The following references are of record in the file ofthis patent:

of the group consisting Certificate of Correction Patent No. 2,528,654November 7 1950 SIMON H. HERZFELD ET AL.

It is hereby certified that error appears in the printed specificationof the above numbered patent requiring correction as follows:

Column 2, line 15, for the Word chlorine read chloniene;

and that the said Letters Patent should be read as corrected above, sothat the same may conform to the record of the case in the PatentOffice. Signed and sealed this 16th day of January, A. D. 1951.

THOMAS F. MURPHY, A

Assistant Gammim'mwr of Patents.

1. A NEW COMPOSITION OF MATTER HAVING THE STRUCTURAL FORMULA